US6013408A - Silver halide light-sensitive material comprising support, hardening layer and light-sensitive layer - Google Patents
Silver halide light-sensitive material comprising support, hardening layer and light-sensitive layer Download PDFInfo
- Publication number
- US6013408A US6013408A US09/136,686 US13668698A US6013408A US 6013408 A US6013408 A US 6013408A US 13668698 A US13668698 A US 13668698A US 6013408 A US6013408 A US 6013408A
- Authority
- US
- United States
- Prior art keywords
- group
- light
- silver halide
- layer
- sensitive material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- -1 Silver halide Chemical class 0.000 title claims abstract description 177
- 239000000463 material Substances 0.000 title claims abstract description 108
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 101
- 239000004332 silver Substances 0.000 title claims abstract description 101
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- 125000001424 substituent group Chemical group 0.000 claims abstract description 36
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 28
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 28
- 238000007127 saponification reaction Methods 0.000 claims abstract description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 15
- 125000005647 linker group Chemical group 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims description 52
- 125000004432 carbon atom Chemical group C* 0.000 claims description 39
- 125000001931 aliphatic group Chemical group 0.000 claims description 37
- 125000000623 heterocyclic group Chemical group 0.000 claims description 35
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 157
- 238000011161 development Methods 0.000 description 38
- 229910052782 aluminium Inorganic materials 0.000 description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 34
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 32
- 239000002585 base Substances 0.000 description 30
- 239000000839 emulsion Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 27
- 230000006870 function Effects 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 26
- 239000000975 dye Substances 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 21
- 239000002253 acid Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 229920001477 hydrophilic polymer Polymers 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- 238000011160 research Methods 0.000 description 10
- 230000001235 sensitizing effect Effects 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- 125000002252 acyl group Chemical group 0.000 description 8
- 125000004423 acyloxy group Chemical group 0.000 description 8
- 125000003277 amino group Chemical group 0.000 description 8
- 239000003086 colorant Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 238000007743 anodising Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 230000003595 spectral effect Effects 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- 239000006224 matting agent Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 206010070834 Sensitisation Diseases 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
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- 238000005530 etching Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 4
- 125000004450 alkenylene group Chemical group 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 235000013877 carbamide Nutrition 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- 150000002504 iridium compounds Chemical class 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 229910052913 potassium silicate Inorganic materials 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 150000003284 rhodium compounds Chemical class 0.000 description 4
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 125000000547 substituted alkyl group Chemical group 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 239000004111 Potassium silicate Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910021612 Silver iodide Inorganic materials 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
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- 150000001412 amines Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 3
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- 230000003993 interaction Effects 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
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- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 3
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- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical group [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- DILDNVWLJWRKFK-UHFFFAOYSA-M silver;sulfanide Chemical class [SH-].[Ag+] DILDNVWLJWRKFK-UHFFFAOYSA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000004426 substituted alkynyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000005649 substituted arylene group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/0285—Silver salts, e.g. a latent silver salt image
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
- G03C8/40—Development by heat ; Photo-thermographic processes
- G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
- G03C8/408—Additives or processing agents not provided for in groups G03C8/402 - G03C8/4046
Definitions
- the present invention relates to a silver halide light-sensitive material comprising a support, a hardening layer and a light-sensitive layer.
- U.S. Pat. No. 4,629,676 (Hayakawa et al.) and European Patent No. 0174634 (Fuji Photo Film Co., Ltd.) disclose an image forming method comprising the steps of imagewise exposing to light a light-sensitive material and heating the light-sensitive material.
- the light-sensitive material comprises a support and a light-sensitive hardening layer containing silver halide, a reducing agent and a polymerizable compound.
- the silver halide is developed by heating the light-sensitive material to form a polymer image.
- the polymerization is initiated by an oxidation radical of the reducing agent (including a radical formed from an oxidation product of the reducing agent).
- the light-sensitive hardening layer preferably comprises a hardening layer and a light-sensitive layer.
- the hardening layer contains a polymerizable compound or a cross-linkable polymer.
- the light-sensitive layer contains silver halide.
- the hardening layer or the light-sensitive layer further contains a reducing agent.
- the light-sensitive material can further comprise an over-coating layer provided on the light-sensitive layer.
- a process for the preparation of a lithographic plate comprises the steps of imagewise exposing to light the light-sensitive material, heating the material, and removing the light-sensitive layer and the unhardened area of the hardening layer with an alkaline etching solution.
- the formed replica image is used as a printing plate.
- U.S. Pat. No. 5,122,443 (Takeda), 5,290,659 (Takeda) and European Patent No. 0426192 (Fuji Photo Film Co., Ltd.) propose to use polyvinyl alcohol having a high saponification degree as a binder of the light-sensitive layer or the overcoating layer.
- the polyvinyl alcohol of the high saponification degree has a function of preventing oxygen from permeating into the hardening layer.
- the polyvinyl alcohol of the high saponification degree has another function of protecting components of the light-sensitive material (e.g., a reducing agent) from oxygen in the air while storing the material.
- the applicant has studied the silver halide light-sensitive material to use the formed replica image as a printing plate.
- a silver halide light-sensitive material for practical use needs a latitude in a processing condition.
- the light-sensitive material is not always process at the optimum condition at a practical stage, which is different from an experimental stage. It is difficult to practically use a light-sensitive material that forms an image of low quality at a condition slightly different from the optimum condition, even though the material forms an image of high quality at the optimum condition at the experimental stage.
- the most important processing condition is the heating temperature at the heat development.
- An object of the present invention is to enlarge the latitude in a processing condition.
- Another object of the invention is to provide a silver halide light-sensitive material that forms a clear image (a sufficiently hardened replica image) even if the heating temperature is relatively low.
- the present invention provides a silver halide light-sensitive material comprising a support, a hardening layer, a light-sensitive layer and an overcoating layer in the order, said hardening layer containing an ethylenically unsaturated polymerizable compound or an ethylenically unsaturated cross-linkable polymer, said light-sensitive layer containing silver halide, said overcoating layer containing polyvinyl alcohol having a saponification degree of not less than 90%, and said hardening layer or said light-sensitive layer containing a reducing agent, wherein the hardening layer or the light-sensitive layer further contains a phenol compound represented by the formula (I): ##STR2## in which L 1 is a divalent linking group selected from the group consisting of --S--, --O--, --CO--, --SO--, --SO 2 --, --NR 1 --, a divalent aliphatic group, a divalent aromatic group, a divalent heterocyclic group and a combination thereof;
- the invention also provides a silver halide light-sensitive material comprising a support, a hardening layer and a light-sensitive layer in the order, said hardening layer containing an ethylenically unsaturated polymerizable compound or an ethylenically unsaturated cross-linkable polymer, said light-sensitive layer containing silver halide and polyvinyl alcohol having a saponification degree of not less than 90%, and said hardening layer or said light-sensitive layer containing a reducing agent, wherein the hardening layer or the light-sensitive layer further contains a phenol compound represented by the formula (I).
- the present invention is characterized in that the hardening layer or the light-sensitive layer further contains a phenol compound represented by the formula (I).
- the phenol compound has a function of lowering a heating temperature for the heat development. Therefore, the silver halide light-sensitive material of the present invention can form a clear image (a sufficiently hardened replica image) even if the heating temperature is relatively low.
- the latitude of the heat development temperature is enlarged in the silver halide light-sensitive material of the present invention. Accordingly, the silver halide light-sensitive material is now suitable for practical use.
- the silver halide light-sensitive material has another advantage of saving the energy for the heat development.
- the phenol compound represented by the formula (I) has been known as an antioxidant of protecting a component of a light-sensitive material (e.g., a reducing agent) from oxygen in the air, as is described in Japanese Patent Provisional Publication No. 1(1989)-177029. Further, Japanese Patent Provisional Publication No. 4(1992)-116659 describes that the phenol compound is used at a heat development of a light-sensitive material containing silver halide, a reducing agent and a polymerizable compound. The phenol compound is used to protect a polymerization reaction of the polymerizable compound from oxygen in the air, which has a function of inhibiting the polymerization reaction.
- a light-sensitive material e.g., a reducing agent
- the silver halide light-sensitive material contains polyvinyl alcohol having a high saponification degree, which has a function of protecting the components of the light-sensitive material and the image forming reactions from oxygen in the air.
- polyvinyl alcohol having a high saponification degree was experimentally proved. Therefore, the silver halide light-sensitive material using the polyvinyl alcohol is free from the problems caused by oxygen in the air.
- the applicant has surprisingly found the new function of the phenol compound, namely the function of lowering the heat development temperature, which is effective in the silver halide light sensitive material that is free from the problems caused by oxygen in the air.
- the new function of the phenol compound and the new effect of the present invention are completely different from the known function of the phenol compound, that is the function of protecting the components of the light-sensitive material and the image forming reactions from oxygen in the air.
- FIG. 1 is a sectional view schematically illustrating a preferred embodiment of a silver halide light-sensitive material.
- FIG. 2 is a sectional view schematically illustrating another preferred embodiment of a silver halide light-sensitive material.
- the phenol compound used in the present invention is represented by the formula (I): ##STR3##
- L 1 is a divalent linking group selected from the group consisting of --S--, --O--, --CO--, --SO--, --SO 2 --, --NR 1 --, a divalent aliphatic group, a divalent aromatic group, a divalent heterocyclic group and a combination thereof.
- R 1 is hydrogen, an alkyl group or an aryl group.
- R 1 preferably is hydrogen or an alkyl group, and more preferably is hydrogen.
- the alkyl group preferably has a chain structure rather than a cyclic structure.
- the alkyl group of the chain structure may be branched.
- the alkyl group preferably has 1 to 6 carbon atoms, more preferably has 1 to 4 carbon atoms, further preferably has 1 to 3 carbon atoms, and most preferably has 1 or 2 carbon atoms.
- the aryl group preferably has 6 to 30 carbon atoms, more preferably has 6 to 20 carbon atoms, further preferably has 6 to 15 carbon atoms, and most preferably has 6 to 10 carbon atoms.
- the divalent aliphatic groups include an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group and a substituted alkynylene group.
- the alkylene group, the substituted alkylene group, the alkenylene group and the substituted alkenylene group are preferred, and the alkylene group and the substituted alkylene group are more preferred.
- the number of the total carbon atoms of the divalent aliphatic group is preferably in the range of 1 to 40, more preferably in the range of 1 to 20, further preferably in the range of 2 to 18, and most preferably in the range of 2 to 15.
- the number of the carbon atoms of the divalent aliphatic group is preferably in the range of 1 to 20, more preferably in the range of 1 to 15, further preferably in the range of 1 to 10, and most preferably in the range of 1 to 6.
- the divalent aliphatic group preferably has a chain structure rather than a cyclic structure.
- the divalent aliphatic group of the chain structure may be branched.
- the divalent aromatic groups include an arylene group and a substituted arylene group.
- arylene groups include phenylene and naphthylene. Phenylene is preferred, and 1,3-phenylene is particularly preferred.
- the number of the total carbon atoms of the divalent aromatic group (including a substituent group) is preferably in the range of 6 to 60, more preferably in the range of 6 to 40, further preferably in the range of 6 to 30, furthermore preferably in the range of 6 to 20, and most preferably in the range of 6 to 12.
- the divalent heterocyclic group preferably has a five-membered, six-membered or seven-membered ring, more preferably has a five-membered or six-membered ring, and most preferably has a six-membered ring.
- the hetero atoms include nitrogen, oxygen and sulfur.
- An aliphatic ring, an aromatic ring or another heterocyclic ring may be condensed with or combined by a spiro union to the ring of the divalent heterocyclic group.
- the divalent heterocyclic group may have a substituent group.
- the number of the total carbon atoms of the divalent heterocyclic group (including a substituent group) is preferably in the range of 1 to 50, more preferably in the range of 2 to 40, further preferably in the range of 2 to 30, furthermore preferably in the range of 3 to 20, and most preferably in the range of 3 to 12.
- substituent groups of the divalent aliphatic, aromatic or heterocyclic groups include hydroxyl, a halogen atom (e.g., chloride), cyano, amino, a substituted amino group, a heterocyclic group, an acyl group and an acyloxy group.
- the substituent group of the substituted amino group is an aliphatic group or an aromatic group.
- the acyl group is defined as --CO--R (wherein R is an aliphatic group, an aromatic group or a heterocyclic group).
- the acyloxy group is defined as --O--CO--R (wherein R is an aliphatic group, an aromatic group or a heterocyclic group).
- Examples of the substituent groups of the divalent aromatic or heterocyclic groups further include an aliphatic group.
- the definitions and examples of the aliphatic, aromatic and heterocyclic groups are the same as those of the substituent groups of the benzene rings A 1 and B 1 .
- L17 --AL--O--CO--AL--Hc--AL--CO--O--AL--
- each of R 11 and R 12 independently has the same meanings as those of R 1 .
- each of the benzene rings A 1 and B 1 may have one to four substituent groups.
- substituent groups examples include hydroxyl, a halogen atom (e.g., chloride), cyano, amino, a substituted amino group, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group and an acyloxy group.
- the substituent group of the substituted amino group is an aliphatic group or an aromatic group.
- the acyl group is defined as --CO--R (wherein R is an aliphatic group, an aromatic group or a heterocyclic group).
- the acyloxy group is defined as --O--CO--R (wherein R is an aliphatic group, an aromatic group or a heterocyclic group).
- the aliphatic groups include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group and a substituted aralkyl group.
- the alkyl group, the substituted alkyl group, the alkenyl group, the substituted alkenyl group, the aralkyl group and the substituted aralkyl group are preferred, the alkyl group, the substituted alkyl group, the alkenyl group and the substituted alkenyl group are more preferred, the alkyl group and the substituted alkyl group are further preferred, and the alkyl group is most preferred.
- the number of the total carbon atoms of the aliphatic group is preferably in the range of 1 to 40, more preferably in the range of 1 to 20, further preferably in the range of 1 to 15, and most preferably in the range of 1 to 10.
- the number of the carbon atoms of the aliphatic group is preferably in the range of 1 to 20, more preferably in the range of 1 to 15, further preferably in the range of 1 to 10, and most preferably in the range of 1 to 6.
- the aliphatic group preferably has a chain structure rather than a cyclic structure.
- the aliphatic group of the chain structure may be branched.
- the aromatic groups include an aryl group and a substituted aryl group.
- Examples of the aryl groups include phenyl and naphthyl.
- the number of the total carbon atoms of the aromatic group (including a substituent group) is preferably in the range of 6 to 60, more preferably in the range of 6 to 40, further preferably in the range of 6 to 30, furthermore preferably in the range of 6 to 20, and most preferably in the range of 6 to 12.
- the heterocyclic group preferably has a five-membered, six-membered or seven-membered ring, more preferably has a five-membered or six-membered ring, and most preferably has a six-membered ring.
- the hetero atoms include nitrogen, oxygen and sulfur.
- An aliphatic ring, an aromatic ring or another heterocyclic ring may be condensed with or combined by a Spiro union to the ring of the heterocyclic group.
- the heterocyclic group may have a substituent group.
- the number of the total carbon atoms of the heterocyclic group (including a substituent group) is preferably in the range of 1 to 50, more preferably in the range of 2 to 40, further preferably in the range of 2 to 30, furthermore preferably in the range of 3 to 20, and most preferably in the range of 3 to 12.
- substituent groups of the aliphatic, aromatic or heterocyclic groups include hydroxyl, a halogen atom (e.g., chloride), cyano, amino, a substituted amino group, a heterocyclic group, an acyl group and an acyloxy group.
- the substituent group of the substituted amino group is an aliphatic group or an aromatic group.
- the acyl group is defined as --CO--R (wherein R is an aliphatic group, an aromatic group or a heterocyclic group).
- the acyloxy group is defined as --O--CO--R (wherein R is an aliphatic group, an aromatic group or a heterocyclic group).
- substituent groups of the aromatic or heterocyclic groups further include an aliphatic group.
- the phenol compound preferably is a hindered phenol compound represented by the formula (II).
- the hindered phenol compound means a phenol compound having a bulk substituent group at its ortho position such as a tertiary alkyl group, which causes a steric hindrance. ##STR4##
- L 2 is a divalent linking group selected from the group consisting of --S--, --O--, --CO--, --SO--, --SO 2 --, --NR 2 --, a divalent aliphatic group, a divalent aromatic group, a divalent heterocyclic group and a combination thereof.
- R 2 is hydrogen, an alkyl group or an aryl group.
- R 2 preferably is hydrogen or an alkyl group, and more preferably is hydrogen.
- the alkyl group preferably has a chain structure rather than a cyclic structure.
- the alkyl group of the chain structure may be branched.
- the alkyl group preferably has 1 to 6 carbon atoms, more preferably has 1 to 4 carbon atoms, further preferably has 1 to 3 carbon atoms, and most preferably has 1 or 2 carbon atoms.
- the aryl group preferably has 6 to 30 carbon atoms, more preferably has 6 to 20 carbon atoms, further preferably has 6 to 15 carbon atoms, and most preferably has 6 to 10 carbon atoms.
- divalent linking groups are the same as those of L 1 in the formula (I).
- each of R 21 , R 22 , R 23 , R 24 , R 25 and R 26 independently is an alkyl group having 1 to 6 carbon atoms.
- the alkyl group preferably has 1 to 4 carbon atoms, more preferably has 1 to 3 carbon atoms, further preferably has 1 or 2 carbon atoms (methyl or ethyl), and most preferably has 1 carbon atom (methyl).
- each of the benzene rings A 2 and B 2 may have one to three substituent groups.
- substituent groups are the same as those of the substituent groups of the benzene rings Al and B 1 in the formula (I).
- the phenol compound represented by the formula (I) is added to the hardening layer or the light-sensitive layer, and is preferably added to the hardening layer.
- the phenol compound is dissolved or dispersed in a coating solution of the hardening layer or the light-sensitive layer. Whether the phenol compound is dissolved or dispersed depends on a solvent of the coating solution. Further, a solution of the phenol compound in a solvent other than the solvent of the coating solution can be emulsified in the coating solution.
- the amount of the phenol compound is preferably in the range of 0.05 to 20 mol, and more preferably in the range of 0.1 to 1 mol based on 1 mol of the reducing agent.
- the silver halide light-sensitive material comprises a support, a hardening layer and a light-sensitive layer in the order.
- the light-sensitive material can comprise three or more layers such as a hardening layer, a light-sensitive layer and an overcoating layer (or an image formation accelerating layer).
- An adhesive layer may be provided between the hardening layer and the light-sensitive layer.
- a reducing agent is added to the hardening layer or the light-sensitive layer, and is preferably added to the light-sensitive layer.
- Polyvinyl alcohol having a saponification degree of not less than 90% is added to the uppermost layer (an overcoating layer in the case that the overcoating layer is provided or a light-sensitive layer in the case that the light-sensitive layer is not provided).
- the components of the above-mentioned layers are preferably uniformly dispersed in the layers without use of microcapsules.
- the light-sensitive material may further have other optional layers such as an adhesive layer, a strippable layer, an undercoating layer and an intermediate layer.
- FIG. 1 is a sectional view schematically illustrating a preferred embodiment of a silver halide light-sensitive material.
- the light-sensitive material shown in FIG. 1 comprises an aluminum support (1), a hardening layer (2), a light-sensitive layer (3) and an overcoating layer (4) in that order.
- the hardening layer (2) contains a phenol compound (21), an ethylenically unsaturated polymerizable compound (22) and an ethylenically unsaturated cross-linkable polymer (23).
- the light-sensitive layer (3) contains silver halide (31), a reducing agent (32) and a hydrophilic polymer (33).
- the overcoating layer contains a base precursor (41) and polyvinyl alcohol having a saponification degree of not less than 90% (42).
- FIG. 2 is a sectional view schematically illustrating another preferred embodiment of a silver halide light-sensitive material.
- the light-sensitive material shown in FIG. 2 comprises an aluminum support (1), a hardening layer (2) and a light-sensitive layer (3) in the order.
- the hardening layer (2) contains a phenol compound (21), an ethylenically unsaturated polymerizable compound (22) and an ethylenically unsaturated cross-linkable polymer (23).
- the light-sensitive layer (3) contains silver halide (31), a reducing agent (32), a base precursor (33) and polyvinyl alcohol having a saponification degree of not less than 90% (34).
- the support can be made of a paper, a synthetic paper, a paper laminated with a synthetic resin (e.g., polyethylene, polypropylene, polystyrene), a plastic (e.g., polyethylene terephthalate, polycarbonate, polyimide, Nylon, cellulose triacetate) film, a metal (e.g., aluminum, aluminum alloy, zinc, iron, copper) plate or a paper or plastic film laminated with the metal. Further, the metal can be evaporated onto the paper or plastic film to form the support.
- a synthetic resin e.g., polyethylene, polypropylene, polystyrene
- a plastic e.g., polyethylene terephthalate, polycarbonate, polyimide, Nylon, cellulose triacetate
- a metal e.g., aluminum, aluminum alloy, zinc, iron, copper
- the metal can be evaporated onto the paper or plastic film to form the support.
- the support is preferably made of an aluminum plate, a polyethylene terephthalate film, a polycarbonate film, a paper or a synthetic paper.
- a complex sheet can also be used as the support.
- an aluminum sheet can be laminated on the polyethylene terephthalate film.
- the aluminum support is particularly preferred.
- the aluminum support preferably has a thickness in the range of 0.1 to 0.5 mm.
- the aluminum support is preferably treated to form a rough surface (graining treatment) or a hydrophilic surface.
- the treatment for the rough surface can be conducted by an electrochemical graining treatment and/or a mechanical graining treatment.
- a current passes through an aluminum plate in an electrolytic solution of hydrochloric acid or nitric acid.
- the mechanical graining treatment includes a wire brushing method, a ball graining method and a brash graining method.
- the wire brushing method the surface of aluminum plate is scratched with a metal wire.
- the ball graining method the surface of aluminum plate is grained with graining balls and a graining agent.
- the brash graining method the surface is grained with a Nylon brash and a graining agent.
- the grained aluminum plate is then chemically etched with an alkali or an acid.
- An alkali etching method is industrially advantageous.
- the alkali agents include sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, sodium hydroxide, potassium hydroxide and lithium hydroxide.
- the alkali solution preferably has a concentration in the range of 1 to 50 wt.%.
- the temperature of the alkali treatment is preferably in the range of 20 to 100° C.
- the treatment conditions are preferably so adjusted that the amount of the dissolved aluminum is in the range of 5 to 20 g per m 2 .
- the aluminum plate is usually washed with an acid to remove smut from the surface after the alkali etching treatment.
- the acids include nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid and borofluoric acid.
- the smut removing treatment can also be conducted according to a conventional method after the electrochemical graining treatment.
- an aluminum plate can be treated with 15 to 65 wt. % sulfuric acid at a temperature in the range of 50 to 90° C.
- the surface treated aluminum plate can be subjected to an anodizing treatment or a chemical treatment.
- the anodizing treatment can be conducted according to a conventional method.
- a direct or alternative current passes through an aluminum plate in a solution of an acid to form an anodic oxide layer on the surface of the plate.
- the acids include sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid and benzenesulfonic acid.
- the conditions of the anodizing treatment depend on the contents of the electrolytic solution.
- the concentration of the electrolytic solution is preferably in the range of 1 to 80 wt.
- the temperature of the solution is preferably in the range of 5 to 70° C.
- the current density is preferably in the range of 0.5 to 60 A/dm2
- the voltage is preferably in the range of 1 to 100 v
- the time for the electrolysis is preferably in the range of 10 to 100 seconds.
- the anodizing treatment is preferably conducted in sulfuric acid at a high current density.
- Phosphoric acid is also preferably used for the anodizing treatment.
- the aluminum plate can be treated with an alkali metal silicate.
- the aluminum plate can be immersed in an aqueous solution of sodium silicate.
- An undercoating layer can be provided on the aluminum support to improve the adhesion between the support and the hardening layer or to improve a printing character.
- An undercoating layer can be provided on not only the above-mentioned aluminum support, but also a support having a hydrophobic (or not sufficiently hydrophilic) surface (e.g., a polymer film).
- the components of the undercoating layer include a polymer (e.g., gelatin, casein, polyvinyl alcohol, ethyl cellulose, phenol resin, styrene-maleic anhydride resin, polyacrylic acid), an amine (e.g., monoethanol amine, diethanol amine, triethanol amine, tripropanol amine) and a salt thereof (e.g., chloride, oxalate, phosphate), an monoaminomonocarboxylic acid (e.g., aminoacetic acid, alanine), an oxyamino acid (e.g., serine, threonine, dihydroxyethylglycine), a sulfur containing amino acid (e.g., cysteine, cystine), a monoaminodicarboxylic acid (e.g., aspartic acid, glutamic acid), an aromatic amino acid (e.g., p-hydroxylphenylglycine, phenylalanine,
- hydrophilic fine particles e.g., silica particles
- hydrophilic fine particles are preferably added to a hydrophilic undercoating layer in place of the graining treatment of an aluminum support.
- the hardening layer contains an ethylenically unsaturated polymerizable compound or an ethylenically unsaturated cross-linkable polymer.
- the hardening layer preferably contains the polymerizable compound and the cross-linkable polymer.
- the amount of the cross-linkable polymer is preferably in the range of 30 to 95 wt. %, and more preferably in the range of 50 to 90 wt. % based on the amount of the hardening layer.
- the amount of the ethylenically unsaturated polymerizable compound is preferably in the range of 3 to 200 wt. %, and more preferably in the range of 10 to 100 wt. % based on the amount of the cross-linkable polymer.
- the hardening layer preferably has a thickness in the range of 0.1 to 20 ⁇ m, and more preferably in the range of 0.3 to 7 ⁇ m.
- the adhesive layer contains a polymer having a function of improving the adhesion between the hardening layer and the light-sensitive layer.
- the coating amount of the adhesive layer is preferably in the range of 0.01 to 2 g per m 2 , more preferably in the range of 0.02 to 1.5 g per m 2 , and most preferably in the range of 0.025 to 1.0 g per m 2 .
- the light-sensitive layer contains silver halide, and preferably further contains a hydrophilic polymer.
- the coating amount of silver halide is preferably in the range of 0.01 to 5 g per m 2 , more preferably in the range of 0.03 to 1 g per m 2 , and most preferably in the range of 0.05 to 0.3 g per m 2 .
- the light-sensitive layer preferably has a thickness in the range of 0.07 to 13 ⁇ m, and more preferably in the range of 0.2 to 5 ⁇ m.
- An overcoating layer has a function of preventing oxygen in the air from permeating into the hardening layer. Oxygen functions as a polymerization inhibitor.
- the overcoating layer can function as a protective layer.
- the overcoating layer can also function as an image formation accelerating layer, where the layer further contains a component (e.g., a base, a base precursor, a reducing agent, a heat development accelerator) that accelerates an image forming reaction.
- the overcoating layer preferably has a thickness in the range of 0.3 to 20 ⁇ m, more preferably in the range of 0.5 to 7 ⁇ m.
- An intermediate layer can be provided between the layers.
- the intermediate layer can function as an antihalation layer. a filter layer or a barrier layer.
- the antihalation layer and the filter layer is a functional layer containing a dye.
- the barrier layer prevents components from moving between layers when the light-sensitive material is stored.
- the composition of the intermediate layer is determined according to its function.
- the intermediate layer preferably has a thickness of not more than 10 ⁇ m.
- Silver halide is silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide or silver chloroiodobromide in the form of grains.
- the crystal forms of silver halide grains preferably are cubic or tetradecahedron. Irregular forms and mixed forms as well as the above mentioned regular forms can be used in the silver halide emulsions. Examples of the irregular forms include a potato-like form, a spherical form and a tabular form.
- the tabular form usually has an aspect ratio (diameter per thickness) of 5 or more.
- the silver halide grains may be extremely small grains having a grain diameter (diameter of projected area) of less than 0.01 ⁇ m.
- the grains may also be relatively large grains having a diameter of more 10 ⁇ m.
- a monodispersed emulsion is preferred to a polydispersed emulsion. The monodispersed emulsion is described in U.S. Pat. Nos. 3,574,628, 3,655,394 and British Patent No. 1,413,748.
- the individual grains have a homogeneous halogen composition or a heterogeneous halogen composition.
- the composition varies from the outer surface portion to the inside portion.
- the grains may have a multi-layered structure.
- the silver halide grains may be conjugated with other silver halide grains having different halogen composition through epitaxial conjugation.
- the grains may be conjugated with compounds other than the silver halide such as silver rhodanate and lead oxide.
- salts can be added to the silver halide grains.
- the substances include copper, thallium, lead, cadmium, zinc, chalcogens (e.g., sulfur, selenium, tellurium), gold, and noble metals of group VIII (e.g., rhodium, iridium, iron, platinum, palladium).
- the salts are added to the emulsion at the grain formation or after the grain formation according to a conventional process. The conventional process is described in U.S. Pat. Nos.
- the silver halide grains can be doped with iridium ion by adding an aqueous solution of an iridium compound to a silver halide emulsion.
- water-soluble iridium compounds include hexachloroiridic(III) salts and hexachloroiridic(IV) salts.
- the silver halide grains can also be doped with rhodium ion by adding an aqueous solution of a rhodium compound to a silver halide emulsion.
- water-soluble rhodium compounds include rhodium ammonium chloride, rhodium trichloride and rhodium chloride.
- the iridium compound or the rhodium compound can be dissolved in a halide solution for forming silver halide grains.
- the aqueous solution of the iridium compound or the rhodium compound can be used before or after the grain formation. Further, the solution can be added to the emulsion between the grain formation and a chemical sensitization. The solution is preferably added at the stage of the grain formation.
- the iridium or rhodium ion is preferably used in an amount of 10 -8 to 10 -3 mol, and more preferably in an amount of 10 -7 to 10 -5 mol based on 1 mol of silver halide.
- Two or more kinds of silver halide grains that differ in halogen composition, crystal habit, grain size, or other features from each other can be used in combination.
- the silver halide is preferably used in the form of an emulsion.
- the silver halide emulsion can be prepared by known processes, which are described in Research Disclosure (RD), No. 17,643, pages 22 to 23 (December 1978), (Emulsion preparation and types); and Research Disclosure, No. 18,716, page 648, (November 1979).
- the silver halide emulsion is generally used after a physical ripening and a chemical sensitization.
- the silver halide grains preferably have a low fogging value.
- additives can be used in the ripening or sensitizing steps.
- the additives are described in Research Disclosure, No. 17,643 and No. 18,716.
- the chemical sensitizer is described in No. 17,643 (page 23) and No. 18,716 (page 648, right column).
- Other additives are also described in Research Disclosure.
- a sensitivity-increasing agent is described in No. 18,716 (page 648, right column).
- An anti-fogging agent and a stabilizer are described in No. 17,643 (pages 24 to 25) and No. 18,716 (page 649, right column), respectively.
- the silver halide emulsion is usually subjected to a spectral sensitization.
- Various spectral sensitizing dyes are known in a conventional silver halide photography. Examples of the sensitizing dyes include cyanine dyes, merocyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
- the spectral sensitizing dyes can be used to adjust the spectral sensitivity of the light-sensitive material to wavelength of two or more light sources such as various laser beams (e.g., semiconductor laser, helium neon laser, argon ion laser, helium cadmium laser, YAG laser) and a light emission diode.
- various laser beams e.g., semiconductor laser, helium neon laser, argon ion laser, helium cadmium laser, YAG laser
- two or more sensitizing dyes are used for silver halide grains in a light-sensitive layer so that a light-sensitive material can be exposed to two or more light sources.
- a supersensitizer can be added to the emulsion in addition to the sensitizing dye.
- the supersensitizer itself has neither a spectral sensitization effect nor an absorption of visible light, but shows a supersensitizing effect on the sensitizing dye.
- An organic metallic salt can be added to the light-sensitive layer containing silver halide.
- An organic silver salt is particularly preferred.
- organic moieties of the salts include triazoles, tetrazoles, imidazoles, indazoles, thiazoles, thiadiazoles, azaindenes.
- An aliphatic, aromatic or heterocyclic compound having a mercapto group can also be used as the organic moiety.
- silver carboxylates and acetylene silver can be used as the organic silver salt.
- Two or more organic metallic salts can be used in combination.
- the organic silver salt is generally used in an amount of 10 -5 to 10 mol, and preferably 10 -4 to 1 mol based on 1 mol of silver halide.
- the reducing agent has a function of reducing the silver halide or a function of accelerating a hardening reaction of a polymerizable compound or a cross-linkable polymer.
- reducing agents examples include hydrazines (including hydrazides), hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones, 5-aminouracils, 4,5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols, 2,4-disulfonamidephenols, 2,4-disulfonamidenaphthols, o- or p-acylaminophenols, 2-sulfonamidoindanones, 4-sulfonamido-5-pyrazolones, 3-sulfonamidoindoles, sulfonamidopyrazolobenzimidazoles, sulfonamidopyrazol
- R 31 is hydrogen, an alkyl group or an aryl group.
- R 31 preferably is an alkyl group or an aryl group, and more preferably is an aryl group.
- the alkyl group preferably has a chain structure rather than a cyclic structure.
- the alkyl group of the chain structure may be branched.
- the alkyl group preferably has 1 to 6 carbon atoms, more preferably has 1 to 4 carbon atoms, further preferably has 1 to 3 carbon atoms, and most preferably has 1 or 2 carbon atoms.
- the aryl group preferably has 6 to 30 carbon atoms, more preferably has 6 to 20 carbon atoms, further preferably has 6 to 15 carbon atoms, and most preferably has 6 to 10 carbon atoms.
- the alkyl group and the aryl group may have a substituent group.
- the substituent groups include hydroxyl, a halogen atom (e.g., chloride), cyano, amino, a substituted amino group, a heterocyclic group, an acyl group and an acyloxy group.
- An aryl group substituted with chloride is particularly preferred.
- the benzene ring C may have one to five substituent groups.
- substituent groups include hydroxyl, a halogen atom (e.g., chloride), cyano, amino, a substituted amino group, a heterocyclic group, an acyl group and an acyloxy group.
- the benzene ring C is preferably substituted with chloride.
- the reducing agents are described in Japanese Patent Provisional Publication Nos. 61(1986)-183640, 61(1986)-183535, 61(1986)-228441, 62(1987)-70836, 61(1987)-86354, 62(1987)-86355, 62(1987)-206540, 62(1987)-264041, 62(1987)-109437, 63(1988)-254442, 1(1989)-267536, 2(1990)-141756, 2(1990)-141757, 2(1990)-207254, 2(1990)-262662 and 2(1990)-269352.
- the reducing agents are also described in T.
- a reducing agent precursor can be used as the reducing agent.
- the precursor (described in Japanese Patent Provisional Publication No. 62(1987)-210446) can release a reducing agent under heating or in contact with a base.
- the reducing agent When the reducing agent is basic, that is, it forms a salt with an acid, the reducing agent can be used in the form of a salt with an acid.
- the reducing agents can be used singly or in combination. Certain interactions between those reducing agents may be expected where two or more reducing agents are used in combination. One of the interactions is for an acceleration of reduction of silver halide (or an organic silver salt) through so-called super-additivity.
- the other interaction is for a chain reaction between an oxidant of one reducing agent formed by a reduction of silver halide (or an organic silver salt) oxidation-reduction reaction and another reducing agent. The chain reaction induces the polymerization of the polymerizable compound.
- the reducing agent is used in an amount of 0.1 to 10 mol, and more preferably 0.25 to 2.5 mol based on 1 mol of silver halide.
- Antifogging agent silver development accelerator, stabilizer
- the light-sensitive material can contain an antifogging agent, a silver development accelerator or a stabilizer.
- these compounds include mercapto compounds (described in Japanese Patent Provisional Publication No. 59(1984)-111636), azoles or azaindenes (described in Research Disclosure No. 17643 (1978), pages 24 to 25), nitrogen-containing carboxylic acids or the phosphoric acids (described in Japanese Patent Provisional Publication No. 59(1984)-168442), acetylene compounds (described in Japanese Patent Provisional Publication No. 62(1987)-87957) and sulfonamides (described in Japanese Patent Provisional Publication No. 61(1987)-178232).
- An aromatic (a carbon or heterocyclic ring) mercapto compound can also be used as an antifogging agent or a silver development accelerator.
- An aromatic heterocyclic mercapto compound, particularly a mercapto triazole derivative is preferred.
- the mercapto compound can be used in the form of a mercapto silver (silver salt).
- These compounds are generally used in an amount of 10 7 to 1 mol based on 1 mol of the silver halide.
- a hydrophilic polymer is used as a binder of a hydrophilic layer, such as a light-sensitive layer, an overcoating layer and an intermediate layer.
- the hydrophilic polymer has a hydrophilic group or a hydrophilic bond in its molecule.
- the hydrophilic group include carboxyl, hydroxyl (including alcohol and phenol), sulfo, sulfonamido, sulfonimido and amido.
- the hydrophilic bond include urethane bond, ether bond and amido bond.
- Natural or synthetic polymers can be used as the hydrophilic polymer.
- the hydrophilic polymers are described in Japanese Patent Provisional Publication No. 5(1993)-249667.
- Polyvinyl alcohol is a particularly preferred hydrophilic polymer.
- Polyvinyl alcohol used in the uppermost layer has a high saponification degree of not lower than 90%, preferably of not lower than 93 %, more preferably of not lower than 95%, further preferably of not lower than 97%, and most preferably of not lower than 98%.
- the polyvinyl alcohol having the high saponification degree has a very low transmission coefficient of oxygen.
- Polyvinyl alcohol may be denatured by copolymerization with another monomer.
- a copolymer of vinyl acetate and another monomer is saponified to form the denatured polyvinyl alcohol.
- Examples of the monomer copolymerized with the vinyl acetate include ethylene, vinyl higher carboxylate, a higher alkyl vinyl ether, methyl methacrylate and acrylamide.
- Polyvinyl alcohol may also be denatured after the saponification. Hydroxyl in polyvinyl alcohol can be modified by etheration, esterification or acetylation.
- a cross-linked polyvinyl alcohol can also be used.
- the cross-linking agents include aldehydes, methylol compounds, epoxy compounds, diisocyanates, divinyl compounds, dicarboxylic acids and inorganic cross-linking agents (e.g., boric acids).
- the molecular weight of the hydrophilic polymer is preferably in the range of 3,000 to 500,000.
- the polymerizable compound used in the present invention has an ethylenically unsaturated group.
- Examples of the ethylenically unsaturated polymerizable compounds include acrylic acids, salts thereof, acrylic esters, acrylamides, methacrylic acids, salts thereof, methacrylic esters, methacrylamides, maleic anhydride, maleic esters, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocyclic compounds, allyl ethers, allyl esters, and derivatives thereof.
- Acrylic esters and methacrylic esters are preferred.
- examples of the (meth)acrylic esters include pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polyester (meth)acrylate and polyurethane (meth)acrylate.
- Two or more ethylenically unsaturated polymerizable compounds can be used in combination.
- a hydrophilic polymer preferably has a cross-linkable functional group.
- the cross-linkable functional group can be introduced into the main chain or side chain of the polymer molecule.
- the cross-linkable functional group can also be introduced into the polymer by copolymerization.
- polystyrene resin examples include poly-1,4-butadiene, poly-1,4-isoprene and natural or synthetic rubbers.
- polymers of acrylic or methacrylic ester or amide having a specific residue which means R of --COOR (ester) or --CONHR (amide).
- each of R 1 , R 2 and R 3 independently is hydrogen, a halogen atom, an alkyl group, an aryl group, an alkoxy group and aryloxy group.
- R 1 , R 2 or R 3 The number of the carbon atoms contained in R 1 , R 2 or R 3 is not more than 20. R 1 and R 2 or R 3 may be combined to form a ring. In the formulas, n is an integer of 1 to 10. X is dicyclopentadienyl.
- ester residues examples include --CH 2 CH ⁇ CH 2 (described in Japanese Patent Publication No. 7(1995)-21633), --CH 2 CH 2 O--CH 2 CH ⁇ CH 2 , --CH 2 C(CH 3 ) ⁇ CH 2 , --CH 2 CH ⁇ CH--C 6 H 5 , --CH 2 CH 2 OCOCH ⁇ CH--C 6 H 5 , --CH 2 CH 2 --NHCOO--CH 2 CH ⁇ CH 2 and --CH 2 CH 2 O--X (wherein X is dicyclopentadienyl).
- amide residues include --CH 2 CH ⁇ CH 2 , --CH 2 CH 2 --1---Y (wherein Y is cyclohexene) and --CH 2 CH 2 --OCO--CH ⁇ CH 2 .
- the cross-linkable polymer is hardened by adding a free radical to the unsaturated bond (or group).
- the free radical functions as a polymerization initiator or a chain extender.
- the polymers are cross-linked with each other directly or by a chain reaction of a polymerizable compound.
- the polymer can also be cross-linked by a reaction of polymer radicals, which are formed by detaching an atom of the polymers (e.g., hydrogen attached to carbon adjacent to the unsaturated bond) by a free radical.
- non-cross-linkable (or weak cross-linkable) hydrophobic polymers examples include polyacrylic esters, polymethacrylic esters (e.g., polymethyl methacrylate, polybenzyl methacrylate), polyacrylamides and polymethacrylamides. These polymers have a saturated aliphatic residue or an aromatic residue in place of the above-mentioned ethylenically unsaturated residue (R).
- non-cross-linkable polymers include polyacrylic esters, polymethacrylic esters, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polymethacrylonitrile, polyethylene, polyvinyl pyridine, polyvinyl imidazole, polyvinyl butyral, polyvinyl formal, polyvinyl pyrrolidone, chlorinated polyethylene, chlorinated polypropylene, polyesters, polyamides, polyurethanes, polycarbonates, cellulose ether (e.g., ethyl cellulose) and cellulose esters (e.g., triacetyl cellulose, diacetyl cellulose, cellulose acetate butyrate).
- cellulose ether e.g., ethyl cellulose
- cellulose esters e.g., triacetyl cellulose, diacetyl cellulose, cellulose acetate butyrate
- An acidic group is preferably introduced into the above-mentioned hydrophobic (cross-linkable or non-crosslinkable) polymer.
- the acidic functional groups include carboxyl, an acid anhydride group, phenolic hydroxyl, sulfo, sulfonamido and sulfonimido.
- the acidic functional groups can be introduced into the polymer by copolymerization with an acidic monomer.
- the acidic monomers include acrylic acid, methacrylic acid, styrenesulfonic acid and maleic anhydride.
- the amount of the monomer having the acidic functional group is preferably in the range of 1 to 60 mol %, more preferably in the range of 5 to 50 mol % and most preferably in the range of 10 to 40 mol %.
- the molecular weight of the hydrophobic polymer is preferably in the range of 1,000 to 500,000. Two or more polymers can be used in combination.
- the light-sensitive material preferably contains a base or base precursor.
- organic or inorganic bases and their precursors can be used in the light-sensitive material.
- a base precursor is preferred to a base in view of stability of the light-sensitive material.
- An example of the decarboxylation type base precursor is a salt of an organic acid with a base that is decarboxylated under heating (described in Japanese Patent Provisional Publication Nos. 59(1984)-180537, 61(1986)-313431, 63(1988)-316760, 64(1989)-68746).
- An example of the thermal decomposition type base precursor is a urea compound (described in Japanese Patent Provisional Publication No. 63(1988)-96159).
- An example of the reaction type base precursor is a transition metal acetylide (described in Japanese Patent Provisional Publication No. 63(1998)-25208).
- An example of the complex salt-formation type base precursor is a water-insoluble basic metal compound (described in Japanese Patent Provisional Publication No. 1(1989)-3282).
- An example of the dissociation type base precursor is an alkali metal salt of an organic acid (e.g., sodium acetate, sodium salt of a polymer having an acidic group).
- the base precursor preferably releases a base at a temperature in the range of 50 to 200° C., and more preferably in the range of 80 to 160° C.
- the base or the base precursor is preferably used in an amount of preferably 0.1 to 20 mol, and more preferably 0.2 to 10 mol based on 1 mol of silver halide.
- the light-sensitive material can contain a heat development accelerator.
- the heat development accelerator may be added to any layers of the light-sensitive material.
- the heat development accelerator has a function of increasing the plasticity of a polymer (contained in the hardening layer or the light-sensitive layer).
- the accelerator has another function of accelerating the dispersion of the components in the layers when it is dissolved by heat of the development process.
- the heat development accelerator has been known as a plasticizer.
- the known plasticizers are described in Plastic Additives (written in Japanese), pages 21 to 63 (Taisei-sha); Plastics Additives, Second Edition; Hanser Publishers, Chapter 5, pages 251 to 296.
- heat development accelerators examples include polyethers (e.g., polyethylene glycol, polypropylene glycol), polyhydric alcohols (e.g., glycerol, hexanediol), saccharides (e.g., sorbitol), formic esters, ureas (e.g., urea, diethylurea, ethyleneurea), amides (e.g., acetamide, propionamide, malonamide), sulfonamides, urea resins and phenol resins.
- polyethers e.g., polyethylene glycol, polypropylene glycol
- polyhydric alcohols e.g., glycerol, hexanediol
- saccharides e.g., sorbitol
- formic esters ureas (e.g., urea, diethylurea, ethyleneurea)
- amides e.g., acetamide
- the amount of the heat development accelerator is preferably in the range of 0.05 to 2 g per m 2 , and more preferably in the range of 0.1 to 1 g per m 2 .
- the light-sensitive material can contain a colorant.
- the colorant can functions as an antihalation or antiirradiation dye. Further, a hardened image can be colored with the colorant.
- Various known dyes and pigments can be used as the colorant provided that the colorant does not affect the sensitivity and the developing reaction of silver halide.
- the hue of the antihalation or antiirradiation dye is preferably adjusted within the sensitive light region of silver halide.
- the colorants are described in various publications such as Japanese Patent Provisional Publication No. 5(1993)-249667, Handbook of Color Index and New Handbook of Pigments, Nippon Ganryo Gijutsu Kyokai (1970).
- the antiirradiation dyes having little effects on the sensitivity of silver halide are described in Japanese Patent Publication Nos. 41(1966)-20389, 43(1968)-3504, 43(1968)-13168, Japanese Provisional Publication No. 2(1990)-39042, U.S. Pat. Nos. 2,865,752, 3,423,207, 3,697,037, and British Patent Nos. 1,030,392, 1,100,546.
- the amount of the colorant is usually in the range of 0.01 to 2 g per m 2 , and preferably in the range of 0.05 to 1 g per m 2 .
- the development stopping agent can be used in the light-sensitive material to obtain a clear image constantly regardless of the temperature and time for the development process.
- the development stopping agent can be a compound having a function of neutralizing a base or reacting with a base to reduce the base concentration in the layer to stop development.
- the agent can also be a compound having a function of mutually reacting with silver or a silver salt to suppress development, after the appropriate development.
- development stopping agents examples include acid precursors capable of releasing acids upon heating, electrophilic compounds capable of undergoing substitution reaction with a coexisting base upon heating, nitrogen-containing heterocyclic compounds, mercapto compounds, and precursors thereof.
- the development stopping agents are described in Japanese Patent Provisional Publication Nos. 62(1987)-253159, 2(1990)-42447 and 2(1990)-262661.
- a surface active agent can be added to a layer of the light-sensitive material.
- Various nonionic, anionic, cationic or fluorine surface active agents can be used.
- the surface active agent is described in Japanese Patent Provisional Publication No. 2(1990)-195356. Sorbitan, polyoxyethylene and a fluorine-containing compound are preferred.
- a matting agent can be added to a back layer, an overcoating layer or an image formation accelerating layer to prevent adhesion of between two light-sensitive materials when the materials are superposed.
- Inorganic or organic solid particles can be used as the matting agent.
- the matting agents include oxides (e.g., silicon dioxide), alkali earth metal salts, natural polymers (e.g., starch, cellulose) and synthetic polymers.
- the average particle size of the matting agent is preferably in the range of 1 to 50 ⁇ m.
- the amount of the matting agent is preferably in the range of 0.01 to 1 g per M 2 .
- a polymerization inhibitor can be added to the polymerizable layer to prevent a polymerization reaction while storing the light-sensitive material.
- the polymerization inhibitors include nitrosoamines, ureas, thioureas, thioamides, phenols and amines.
- the silver halide light-sensitive is imagewise exposed to light.
- the wavelength of the light corresponds to the spectral sensitivity of silver halide.
- the wavelength is usually within the visible, near ultraviolet and near infrared regions.
- a X-ray and an electron bean can also be used as the light.
- Examples of the light sources include a tungsten lamp, a halogen lamp, a xenon lamp, a xenon flash lamp, a mercury lamp, a carbon arc lamp, various laser means (e.g., semiconductor laser, helium neon laser, argon ion laser, helium cadmium laser), light emitting diode and cathode-ray tube.
- various laser means e.g., semiconductor laser, helium neon laser, argon ion laser, helium cadmium laser
- light emitting diode and cathode-ray tube examples include a tungsten lamp, a halogen lamp, a xenon lamp, a xenon flash lamp, a mercury lamp, a carbon arc lamp, various laser means (e.g., semiconductor laser, helium neon laser, argon ion laser, helium cadmium laser), light emitting diode and cathode-ray tube.
- the amount of the exposure is usually in the range of 0.001 to 1,000 ⁇ J per cm 2 , and preferably in the range of 0.01 to 100 ⁇ J per cm 2 .
- the light-sensitive material can be exposed to light through a transparent support.
- the exposure of silver halide, namely formation of latent image is influenced with the temperature and humidity at the exposing step. Accordingly, the sensitivity depends on the temperature and humidity. Therefore, the temperature and the humidity under the circumstances of the light source and the light-sensitive material are preferably controlled at constant values.
- An image recording apparatus having a controlling device is disclosed in Japanese Patent Provisional Publication Nos. 3(1991)-63143 and 3(1991)-63637.
- the light-sensitive material is developed simultaneously with or after the exposing step.
- the light-sensitive material is preferably heated to develop the silver halide.
- the heat development can be conducted by placing the light-sensitive material on a heated material (e.g., metal plate, block, roller).
- a heated material e.g., metal plate, block, roller.
- the light-sensitive material may be immersed in a heated liquid for the development. Further, the light-sensitive material may be irradiated with an infrared ray.
- the surface of the light-sensitive material may be open to the air while heating the material from the side of the support.
- the surface of the light-sensitive material may be covered with the heating means to prevent the air from penetrating into the layers.
- the heating temperature is preferably in the range of 60 to 200° C., and more preferably in the range of 100 to 150° C.
- the heating time is preferably in the range of 1 to 180 seconds, and more preferably in the range of 5 to 60 seconds.
- a preheat treatment or post-heat treatment can be conducted before or after the heat development.
- the temperature of the preheat is lower than the heat development temperature, and the time is shorter than the development time.
- the post-heat treatment can be conducted after the image is formed, for example after removing the unhardened hardening layer.
- the unhardened area can be selectively removed to form a polymer image based on a difference in the solubility between the hardened area and the unhardened area.
- hydrophilic layers are preferably removed from the light-sensitive material.
- the light-sensitive material is immersed in a solvent (an etching solution) to conduct the removing step.
- a solvent an etching solution
- An alkaline solution is preferably used as the solvent.
- alkaline compound examples include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, sodium phosphate, potassium silicate, ammonia and aminoalcohols (e.g., monoethanolamine, diethanolamine, triethanolamine).
- aminoalcohols e.g., monoethanolamine, diethanolamine, triethanolamine.
- the solvent preferably is water.
- An organic solvent can be used in combination with water.
- An alcohol and an ether are preferably used as the organic solvent.
- the alcohols include lower alcohols (e.g., methanol, ethanol, propanol, butanol), alcohols having an aromatic group (e.g., benzyl alcohol, phenethyl alcohol), polyhydric alcohols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol) and aminoalcohols described above as the alkaline compounds.
- the ethers are cellosolves.
- the solvent may further contain the other additives such as a surface active agent and a defoaming agent.
- the obtained image can be used as a printing plate, a color proof, a hard copy or a relief image.
- the silver halide light-sensitive material can be used to prepare a hard copy, a relief image or a printing plate.
- the light-sensitive material of the present invention is advantageously used for the preparation of a printing plate.
- a surface of an aluminum plate (according to JIS-A-1050) having the thickness of 0.24 mm was ground using a nylon brush and an aqueous suspension of pumice stone of 400 mesh. The plate was well washed out with water. The aluminum plate was then immersed for etching in 10% aqueous solution of sodium hydroxide at 70° C. for 60 seconds. The plate was washed out with running water, then neutralized with 20 wt. % aqueous solution of nitric acid and washed out with water.
- the obtained aluminum plate was subjected to an electrolytic surface-roughening treatment in 1 wt.% aqueous solution of nitric acid containing 0.5 wt.% aluminum nitrate in an anodically electric amount of 160 coulomb per dm 2 using sine wave alternating-corrugated current under such conditions as an anodic voltage of 12.7 V and a cathodically electric amount ratio to an anodically electric amount of 0.9.
- the center line average height (Ra) of the aluminum plate was 0.6 ⁇ m.
- the aluminum plate was immersed in 1 wt. % aqueous solution of sodium hydroxide at 40° C. for 30 seconds. The plate was then immersed in 30 wt. % sulfuric acid at 55° C. for 1 minute. Further, the plate was subjected to anodizing treatment in 20 wt. % aqueous solution of sulfuric acid at a current density of 2 A per dm 2 to form an anodic oxide layer having the thickness of 2.5 g per dm 2 . The plate was washed with water and dried to obtain an aluminum support.
- the following pigment dispersion was prepared.
- the following coating solution was coated and dried on the support to form a hardening layer having the dry thickness of 1.8 ⁇ m.
- Gelatin, potassium bromide and water were placed in a vessel, and the mixture in the vessel was heated to 55° C.
- the following thioether compound (2.0 ⁇ 10 -3 mol based on the total amount of silver nitrate) was added to the vessel.
- an aqueous solution of silver nitrate and an aqueous solution of potassium bromide containing a rhodium ammonium chloride (the molar ratio of rhodium to the total amount of potassium iodide and silver nitrate is 4 ⁇ 10 -8 mol) were added to the vessel according to a pAg controlled double jet method while keeping the pAg of 9.2 in the reaction vessel to prepare a silver iodobromide emulsion.
- a potassium bromide solution containing hexachloroiridate(III) salt (the molar ratio of iridium to silver is 10 -7 mol) was twice added to the emulsion at 55° C. and pAg 8.9 according to a double jet method to obtain a core-shell type silver iodobromide emulsion having the following composition.
- Silver iodobromide (silver iodide content: 7.5 mol%)
- Core/shell 3/7 (molar ratio of silver)
- the grains of the obtained emulsion were monodispersed. In the emulsion, 98% of the grains have a grain size within the range of the average grain size ⁇ 40%.
- the following coating solution was coated and dried on the hardening layer to form a light-sensitive layer having the dry thickness of 1.3 ⁇ m.
- the following coating solution was coated and dried on the light-sensitive layer to form an overcoating layer having the dry thickness of 3.5 ⁇ m.
- the silver halide light-sensitive material was exposed to light of 670 nm through a control wedge (Fuji Photo Film Co., Ltd.), which was attached to the surface of the material.
- the light source was a xenon flush lump.
- the light of 670 nm was spectrally filtered through a sharp cut interference filter.
- the light emission time was 10 -4 second.
- the exposure (energy on the surface) was 2 ⁇ J per cm 2 .
- the aluminum support of the light-sensitive material was placed on a hot plate.
- the material was conveyed on the plate to heat the material for 30 seconds.
- Thus the light-sensitive material was developed.
- the light-sensitive material was washed with water to remove the overcoating layer and the light-sensitive layer.
- the hardening layer was etched with the alkaline solution by a brush in an automatic developing machine.
- the light-sensitive material was well washed with water to form a blue polymer relief image within the exposed area of the hardening layer.
- the experiment was repeated while changing the heating temperature. As a result, a clear image was obtained when the heating temperature (temperature on the surface of the light-sensitive material at the heat development) was 143° C. or higher.
- the clear image means an image in which 3% small dots of 200 line per inch can be observed.
- Example 1 A silver halide light-sensitive material was prepared and evaluated in the same manner as in Example 1, except that the phenol compound (7) was not used in the coating solution of the hardening layer. As a result, the clear image defined in Example 1 was obtained when the heating temperature was 150° C. or higher. The results of Example 1 and Comparison example 1 confirm that the phenol compound (7) has a function of lowering the heating temperature by 7° C.
- Silver halide light-sensitive materials were prepared and evaluated in the same manner as in Example 1, except that the phenol compounds shown in Table 1 was used in place of the phenol compound (7). The amounts of the phenol compounds were the same as the amount of the phenol compound (7). The results are set forth in Table 1. In Table 1, the results of Example 1 and Comparison Example 1 are set forth again.
- the silver halide light-sensitive material prepared in Example 1 was exposed to light of 670 nm.
- the light source was a xenon flush lump.
- the light of 670 nm was spectrally filtered through a sharp cut interference filter.
- the light emission time was 10 -4 second.
- the exposure (energy on the surface) was 2 ⁇ J per cm 2 .
- the aluminum support of the light-sensitive material was placed on a hot plate.
- the material was conveyed on the plate to heat the material for 30 seconds.
- Thus the light-sensitive material was developed.
- the light-sensitive material was connected to an electrode of an LCR meter (4263A, Hewlett Packard).
- the other electrode was connected to an aluminum plate.
- the light-sensitive material and the aluminum plate were immersed in the alkaline solution used in Example 1. After 3 minutes, the current was measured to evaluate permeation of the solution into the hardened image.
- the experiment was repeated while changing the heating temperature. As a result, permeation was not observed (namely the image was sufficiently hardened) when the heating temperature (temperature on the surface of the light-sensitive material at the heat development) was 145° C. or higher.
- the silver halide light-sensitive material prepared in Comparison Example 1 was evaluated in the same manner as in Example 13. As a result, permeation was not observed (namely the image was sufficiently hardened) when the heating temperature (temperature on the surface of the light-sensitive material at the heat development) was 155° C. or higher.
- the results of Example 13 and Comparison example 2 confirm that the phenol compound (7) has a function of lowering the heating temperature.
- a hardening layer was formed on an aluminum support in the same manner as in Example 1.
- the following coating solution was coated and dried on the hardening layer to form a light-sensitive layer having the dry thickness of 3.5 ⁇ m.
- the obtained light-sensitive material was evaluated in the same manner as in Example 1. As a result, the clear image defined in Example 1 was obtained when the heating temperature was 145° C. or higher.
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
______________________________________ Pigment dispersion 15 g Copper phthalocyanine Allyl methacrylate/methacrylic acid copolymer 15 g (copolymerization ratio = 80/20) Methyl ethyl ketone 70 g ______________________________________
______________________________________ Coating solution of hardening layer 2.0 g Pentaerythritol tetraacrylate Allyl methacrylate/methacrylic acid copolymer 4.0 g (copolymerization ratio = 70/30) Phenol compound (7) 0.31 g Propylene glycol monomethyl ether 36.0 g The pigment dispersion 18.0 g ______________________________________
HO--CH.sub.2 CH.sub.2 --S--CH.sub.2 CH.sub.2 --S--CH.sub.2 CH.sub.2 --OH
______________________________________ Coating solution of light-sensitive layer ______________________________________ 10 Wt. % aqueous solution of polyvinyl alcohol having 10.5 g the saponification degree of 88% (PVA-205, Kuraray Co., Ltd.) 0.11 Wt. % agueous solution of the following additive 0.41 g The silver halide emulsion 0.50g 5 Wt. % aqueous solution of the following surface ac- 0.40 g tive agent Water 7.80 g The reducing agent dispersion 1.20 g ______________________________________ ##STR9## Preparation of base precursor dispersion
______________________________________ Coating solution of overcoating layer ______________________________________ 10 Wt. % aqueous solution of polyvinyl alcohol having 200.0 g the saponification degree of 98.5% (PVA-105, Kuraray Co., Ltd.) The base precursor dispersion 1.25g 5 Wt. % aqueous solution of the surface active agent 4.0 g ______________________________________
______________________________________ Alkaline solution ______________________________________ 28 Wt. % aqueous solution of potassium silicate 125.0 g Potassium hydroxide 15.0 g Water 750.0 g ______________________________________
TABLE 1 ______________________________________ Light- Lowest heating sensitive temperature for material Phenol compound forming a clear image ______________________________________ Comp. 1 None 150° C. Example 1 (7) 143° C. Example 2 (1) 145° C. Example 3 (4) 145° C. Example 4 (5) 145° C. Example 5 (6) 143° C. Example 6 (8) 145° C. Example 7 (9) 145° C. Example 8 (10) 145° C. Example 9 (11) 145° C. Example 10 (14) 145° C. Example 11 (20) 145° C. Example 12 (27) 145° C. ______________________________________
______________________________________ Coating solution of light-sensitive layer ______________________________________ 10 Wt. % aqueous solution of polyvinyl alcohol having 200.0 g the saponification degree of 98.5% (FVA-105, Kuraray Co., Ltd.) 0.11 Wt. % aqueous solution of the additive used in 0.41 g Example 1 The silver halide emulsion used in Example 1 0.50g 5 Wt. % aqueous solution of the surface active agent 4.40 g used in Example 1 Water 7.80 g The reducing agent dispersion used in Example 1 1.20 g The base precursor dispersion used in Example 1 1.25 g ______________________________________
Claims (10)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9237790A JPH1165123A (en) | 1997-08-19 | 1997-08-19 | Photosensitive material |
JP9-237790 | 1997-08-19 |
Publications (1)
Publication Number | Publication Date |
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US6013408A true US6013408A (en) | 2000-01-11 |
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ID=17020478
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US09/136,686 Expired - Fee Related US6013408A (en) | 1997-08-19 | 1998-08-19 | Silver halide light-sensitive material comprising support, hardening layer and light-sensitive layer |
Country Status (2)
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US (1) | US6013408A (en) |
JP (1) | JPH1165123A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6156475A (en) * | 1998-12-17 | 2000-12-05 | Fuji Photo Film Co., Ltd. | Image forming process using silver halide, reducing agent and polymerizable compound |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4547450A (en) * | 1982-01-13 | 1985-10-15 | Fuji Photo Film Company | Silver halide sensor type polymerizable light-sensitive material |
JPH01177029A (en) * | 1987-12-28 | 1989-07-13 | Fuji Photo Film Co Ltd | Thermal development photosensitive material |
JPH04116659A (en) * | 1990-09-07 | 1992-04-17 | Fuji Photo Film Co Ltd | Photosensitive material |
US5122443A (en) * | 1989-11-01 | 1992-06-16 | Fuji Photo Film Co., Ltd. | Method of exposing and heating a light-sensitive material comprising polymerizable layer and light-sensitive layer provided on support |
US5171657A (en) * | 1988-10-04 | 1992-12-15 | Canon Kabushiki Kaisha | Light sensitive image forming medium |
US5290659A (en) * | 1990-11-27 | 1994-03-01 | Fuji Photo Film Co., Ltd. | Light-sensitive material comprising light-sensitive layer, polymerizable layer and image formation accelerating layer provided on support |
US5326667A (en) * | 1991-05-07 | 1994-07-05 | Fuji Photo Film Co., Ltd. | Image forming method and light-sensitive material using silver halide, reducing agent and polymerizable compound |
US5843619A (en) * | 1996-09-20 | 1998-12-01 | Fuji Photo Film Co., Ltd. | Silver halide light-sensitive material comprising support, hardening layer and light-sensitive layer |
US5856062A (en) * | 1995-04-18 | 1999-01-05 | Fuji Photo Film Co., Ltd. | Light-sensitive material comprising light-sensitive hardening layer provided on support |
US5882838A (en) * | 1996-10-03 | 1999-03-16 | Fuji Photo Film Co., Ltd. | Silver halide light-sensitive material comprising support, hardening layer and light-sensitive layer |
-
1997
- 1997-08-19 JP JP9237790A patent/JPH1165123A/en not_active Withdrawn
-
1998
- 1998-08-19 US US09/136,686 patent/US6013408A/en not_active Expired - Fee Related
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4547450A (en) * | 1982-01-13 | 1985-10-15 | Fuji Photo Film Company | Silver halide sensor type polymerizable light-sensitive material |
JPH01177029A (en) * | 1987-12-28 | 1989-07-13 | Fuji Photo Film Co Ltd | Thermal development photosensitive material |
US5171657A (en) * | 1988-10-04 | 1992-12-15 | Canon Kabushiki Kaisha | Light sensitive image forming medium |
US5122443A (en) * | 1989-11-01 | 1992-06-16 | Fuji Photo Film Co., Ltd. | Method of exposing and heating a light-sensitive material comprising polymerizable layer and light-sensitive layer provided on support |
JPH04116659A (en) * | 1990-09-07 | 1992-04-17 | Fuji Photo Film Co Ltd | Photosensitive material |
US5290659A (en) * | 1990-11-27 | 1994-03-01 | Fuji Photo Film Co., Ltd. | Light-sensitive material comprising light-sensitive layer, polymerizable layer and image formation accelerating layer provided on support |
US5326667A (en) * | 1991-05-07 | 1994-07-05 | Fuji Photo Film Co., Ltd. | Image forming method and light-sensitive material using silver halide, reducing agent and polymerizable compound |
US5856062A (en) * | 1995-04-18 | 1999-01-05 | Fuji Photo Film Co., Ltd. | Light-sensitive material comprising light-sensitive hardening layer provided on support |
US5843619A (en) * | 1996-09-20 | 1998-12-01 | Fuji Photo Film Co., Ltd. | Silver halide light-sensitive material comprising support, hardening layer and light-sensitive layer |
US5882838A (en) * | 1996-10-03 | 1999-03-16 | Fuji Photo Film Co., Ltd. | Silver halide light-sensitive material comprising support, hardening layer and light-sensitive layer |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6156475A (en) * | 1998-12-17 | 2000-12-05 | Fuji Photo Film Co., Ltd. | Image forming process using silver halide, reducing agent and polymerizable compound |
Also Published As
Publication number | Publication date |
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JPH1165123A (en) | 1999-03-05 |
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